KR20220159184A - Material for high-voltage cable applicable to hydrogen-powered heavy-duty vehicle and preparation method thereof - Google Patents

Abstract

The present invention relates to a heat-resistant resin for manufacturing a high-output, high-capacity cable applicable to hydrogen commercial vehicles, a manufacturing method thereof, and a cable manufactured therefrom.

Description

Material for high-voltage cable applicable to hydrogen-powered heavy-duty vehicle and preparation method thereof}

The present invention relates to a heat-resistant resin for manufacturing a high-output, high-capacity cable applicable to hydrogen commercial vehicles, a manufacturing method thereof, and a cable manufactured therefrom.

Problems such as environmental pollution, climate change, and global warming caused by using fossil fuels, and energy crises due to fossil fuel depletion require mankind to enter a new energy society. The automobile industry, which stands at the center of this change, is in danger of presenting a solution for the future society. In relation to the automobile industry, large-scale national investments are being made in autonomous driving function and eco-friendly vehicle technology, and hydrogen fuel cell vehicles are the main technologies of eco-friendly vehicles along with hybrid electric vehicles and battery electric vehicles. It is regarded as an important growth engine for securing national competitiveness.

Meanwhile, major global organizations are announcing a scenario in which existing internal combustion engine vehicles will be replaced by eco-friendly vehicles at a very rapid pace, and existing internal combustion engine vehicles will be replaced by hybrid vehicles, battery vehicles and hydrogen fuel cell vehicles in turn. are being projected In this context, countries around the world are announcing and promoting aggressive plans to supply hydrogen vehicles with a target of 2030. South Korea also has an aggressive strategy, aiming to supply 6.2 million hydrogen vehicles and 1,200 hydrogen charging stations by 2040. In the case of Europe, a grand plan was presented for entering a hydrogen society through the introduction of not only hydrogen vehicles but also hydrogen fuel cell trains and ships, and China similarly established a strategy to prioritize the introduction of commercial vehicles rather than passenger cars. did This is in consideration of the technical or economic superiority of battery vehicles and hydrogen vehicles, and hydrogen fuel cell trucks are known to have superior economic efficiency compared to battery electric trucks in long-distance driving of more than 100 km.

Commercial vehicles have a longer driving time and distance than passenger cars, so charging time and charging space are very important factors. In addition, since commercial vehicles require a long run at a time compared to passenger cars, large-capacity charging is essential. Commercial hydrogen vehicles are recharged 15 times faster than battery vehicles, and considering this charging time, the turnover rate of charging stations increases, requiring about 10 times less space than battery vehicle charging stations.

In this context, the supply of hydrogen vehicles is carried out along with the supply of charging stations centered on commercial vehicles, and plans are being established and implemented in the direction of large-scale passenger vehicle supply.

Meanwhile, a hydrogen fuel cell system used in a hydrogen vehicle is divided into a hydrogen fuel cell stack corresponding to an engine and a balance of plant required for hydrogen supply, air supply, cooling, and power control of the stack. Similar to conventional internal combustion engine vehicles, the dual driving device utilizes various mechanical parts and materials such as compressors, valves, controllers, and hydrogen compression containers. Economic feasibility can be guaranteed only when technology is secured.

The electrical system of a hydrogen fuel cell vehicle is almost similar to that of an electric vehicle. However, a hydrogen vehicle drives a motor by generating electricity from a hydrogen energy source through a fuel cell, but an electric vehicle drives a motor by directly charging a lithium ion battery from a power grid and then discharging it again.

Specifically, a hydrogen fuel cell vehicle refers to an automobile that drives a motor using electricity generated by an electrochemical reaction between hydrogen and oxygen. Considering that a unit cell has an output voltage of 0.6 to 0.7 V under normal conditions, hundreds of unit cells are connected in series to obtain a high voltage of several hundred volts required to drive an automobile motor. and this is called a stack. A driving device system is essential for the efficient driving of such a fuel cell stack, and because of the use of such a driving device system and high current/high voltage, the electromagnetic characteristics of hydrogen fuel cell vehicles are very different from those of general internal combustion engine vehicles.

Since the voltage of current hydrogen fuel cell vehicles does not always have a constant value and exact specifications have not been determined, the allowable current available for all high current/high voltage cable structures is given as an input value. In addition, this may include a change in voltage or a change in current or voltage value when the inverter output stage motor is driven. In particular, the actuator system includes several sub-systems interconnected by high-current/high-voltage cables. Therefore, a subsystem that is one of the driving system essential for driving the stack may have a fatal effect on other subsystems or driving systems in the driving system through the cable.

The complex electrical wiring of the driving system may cause a fire due to a short circuit in the event of an accident, and high voltage current may flow through the vehicle body in the event of an accident, making it more difficult to extinguish a fire than an internal combustion engine vehicle. In addition, in the case of high-current/high-voltage cables used for driving commercial vehicles such as buses or large trucks, magnetic field radiation is very severe according to Ampere's law of Maxwell's equation. Therefore, it is essential to secure the electromagnetic safety of the driving device system, which is an essential system for the high-current/high-voltage cable for hydrogen fuel cell vehicles.

Accordingly, high-current/high-voltage cables use a braid unlike general cables to shield the electric field, and the effect varies depending on the braiding rate. Since hydrogen commercial vehicles have a higher input (high current/high voltage) value compared to general vehicles, the braided body is an essential structure for high current/high voltage cables.

In addition, the high current/high voltage cable may include an insulating layer made of a polymer composition. At this time, a crosslinkable polymer composition can be used as the polymer composition, which can improve heat resistance, solvent resistance, chemical resistance as well as durability and improve flame retardancy compared to using a thermoplastic material for the insulating layer. .

Therefore, the compound for the insulation coating of the high-current/high-voltage cable for hydrogen commercial vehicles can cross-link molecular chains within the polymer to improve heat resistance stability while maintaining high flame retardancy. Furthermore, mechanical strength and chemical thermal resistance can be improved by cross-linking the polyolefin-based polymer resin with additives.

The polyolefin-based polymer resin can be modified to have desired physical properties or convert a linear molecular structure into a more stable three-dimensional network structure through this crosslinking process.

The insulation coating compound may include a flame retardant. Incombustibility indicators according to the strengthening of safety standards in each country are not only difficult to burn, but also new indicators such as reducing the power of fire, gas, smoke, etc. during combustion to stop combustion and making evacuation and fire extinguishing activities easier are being proposed. , it should not act as a factor that impairs processability and physical properties when mixed with polymer resins. When preparing the insulating polymer composite, it is necessary to select an appropriate flame retardant to induce even dispersion of the flame retardant and auxiliary filler, and to smooth the extruded surface so that the electric field does not concentrate on this part. As such, general flame retardation is achieved by the addition of a flame retardant, and therefore, interest in flame retardants is not only simple flame retardant effect, but also the development of a high flame retardant polymer composition that combines low hazard, low smoke, low corrosion, and heat resistance.

Korea Patent No. 10-1845532, Korean Patent Registration No. 10-1625034.

As a result of intensive research efforts to discover a highly heat-resistant flame retardant thermoplastic elastomer composition applicable to the insulation layer of a large current / high voltage cable for hydrogen commercial vehicles, the inventors of the present invention found that a thermoplastic elastomer composition containing ethene, alkene monomer and diene monomer in a predetermined ratio was found to be vinylsilane It was confirmed that a high-capacity cable for hydrogen commercial vehicles with improved flexibility, flame retardancy, heat resistance and light weight can be provided by introducing a coating layer by mixing with a surface-treated flame retardant and an ethylene copolymer, and crosslinking it to form an insulating layer. The invention was completed.

Each description and embodiment disclosed in the present invention can also be applied to each other description and embodiment. That is, all combinations of the various elements disclosed herein fall within the scope of the present invention. In addition, it cannot be said that the scope of the present invention is limited by the specific description described below.

In addition, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Also, such equivalents are intended to be included in this invention.

In addition, in the entire specification of the present invention, when a part "includes" a certain component, this means that it may further include other components, not excluding other components unless otherwise stated. it means.

Hereinafter, the present invention will be described in more detail.

A first aspect of the present invention provides a thermoplastic elastomer composition comprising ethene, alkene monomer and diene monomer.

The composition may include ethene, alkene monomer and diene monomer in a mass ratio of (28 to 36):(100 to 140):(3 to 17).

For example, the diene monomer is 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4 -Cyclopentyl)-2-norbornene (5-(4-cyclopentenyl)-2-norbornene), 5-cyclohexylidene-2-norbornene (5-cyclohexylidene-2-norbornene), 5-vinyl- 2-norbornene (5-vinyl-2-norbornene), 5-ethylidene-2-norbornene (ethylene-5-ethylidene-2-norbornene), 5-vinylidene-2-norbornene (5- vinylidene-2-norbornene), and a norbornene compound selected from the group consisting of 5-methylene-2-norbornene, but is not limited thereto. Thus, heat resistance and long-term stability can be imparted by using a norbornene compound. When the supply amount of the diene monomer is lower than the above-mentioned ratio, heat resistance may be lowered, and when supplied in excess of the above range, productivity may be lowered.

For example, the alkene monomer is a linear alkene compound selected from the group consisting of propene, butene, pentene, hexene, and octene, or cyclopentene. , cyclohexene, and cyclooctene, but may be a cycloalkene selected from the group consisting of, but is not limited thereto.

A second aspect of the present invention is a thermoplastic elastomer made of ethene, alkene monomer and diene monomer; a flame retardant surface treated with vinylsilane; ethylene copolymer; And a cross-linking agent; provides a cross-linking flame-retardant thermoplastic elastomer composition comprising a.

For example, the cross-linking flame retardant thermoplastic elastomer composition of the present invention may include 18 to 24 parts by weight and 100 to 200 parts by weight of the thermoplastic elastomer and the flame retardant surface-treated with vinylsilane, respectively, based on 100 parts by weight of the ethylene copolymer, but are limited thereto It doesn't work.

Furthermore, the crosslinking type flame retardant thermoplastic elastomer composition of the present invention may include 0.3 to 10% by weight of a crosslinking agent based on the total weight of the thermoplastic elastomer, the flame retardant surface-treated with vinylsilane, and the ethylene copolymer, but is not limited thereto.

For example, the ethylene copolymer is an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer , ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, and ethylene-butyl methacrylate copolymer. It may be selected from the group consisting of, but is not limited thereto. In addition, polymer elastomers such as ethylene propylene copolymer, natural rubber, nitrile butadiene rubber, and chloroprene rubber may be used alone or in combination.

For example, the crosslinking agent is dicumyl peroxide, benzoyl peroxide, 2,5-bis (tert-amylperoxy) -2,5-dimethylhexane (2,5-bis (tert- amylperoxy)-2,5-dimethylhexane), 2,5-bis(tert-butylperoxy) 2,5-dimethylhexane (2,5-bis(tert-butylperoxy) 2,5-dimethylhexane), 3,6- Bis(tert-butylperoxy)-3,6-dimethyloctane (3,6-bis(tert-butylperoxy)-3,6-dimethyloctane), 2,7-bis(tert-butylperoxy)-2,7 -Dimethyloctane (2,7-bis(tert-butylperoxy)-2,7-dimethyloctane), 2,5-bis(tert-butylperoxy)-2,5-dicyclohexylhexane (2,5 bis(tert -butylperoxy) -2,5-dicyclohexylhexane), and an organic peroxide selected from the group consisting of perbutyl peroxide; Triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate selected from the group consisting of irradiated crosslinking agent; or dibutyltin dilaurate, diethyldithiocarbamate, dibutyltin diacetate, triphenyltin acetate, triethyltin cyanide , A silane crosslinking catalyst selected from the group consisting of diphenyltin chloride, and tritolyltin propionate; may be, but is not limited thereto.

For example, the cross-linking flame retardant thermoplastic elastomer composition of the present invention may further include at least one component selected from the group consisting of a mercapto-based heat/oxygen antioxidant, a heat-resistant antioxidant, a discoloration-resistant antioxidant, and an optical brightener. have. Specifically, as the mercapto-based heat/oxygen antioxidant, 3 to 4 parts by weight of zinc 2-mercaptotoluimidazole, zinc 2-mercaptobenzimidazole, zinc 2-mercaptobenzothiazole (zinc 2-mercaptobenzothiazole), zinc 2-mercaptothiobenzothiazole, etc., as a heat-resistant antioxidant, 0.7 to 0.9 parts by weight of tris (2,4-di- Tert-butylphenyl)phosphite (tris(2,4-di-tert-butylphenyl)phosphite), bis(2,4-dicumylphenyl)pentaerythritol diphosphite (bis(2,4-dicumylphenyl)pentaerythritol diphosphite) , bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite), bis (2-tert-butyl-4-methyl-6- Chlorophenyl)-phenyl phosphite (bis(2-tert-butyl-4-methyl-6-chlorophenyl)phenyl phosphite), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (bis(2 ,4-di-tert-butylphenyl)pentaerythritol diphosphite), 2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-tert-butylphenol phosphite (2-butyl-2-ethyl- 1,3-propanediol 2,4,6-tri-tert-butylphenol phosphite), tris(nonylphenyl)phosphite, isodecyl diphenyl phosphite, bis(2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite (bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite), triphenyl phosphite (triph) enyl phosphite), etc., as an anti-discoloration antioxidant, 0.7 to 0.9 parts by weight of tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy phenyl) propionate (tetrakis (methylene (3,5- di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3-di-tert-butyl-4-hydroxyphenyl)propionate) ,5-di-tert-butyl-4-hydroxyphenyl) propionate)), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl)propionate), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate di-tert-butyl-4-hydroxyphenyl)propionate), oxalylbis(azanediyl)bis(ethane-2,1-diyl)bis(3-(3,5-di-tert-butyl-4-hydroxy phenyl)propanoate)(oxalylbis(azanediyl)bis(ethane-2,1-diyl) bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate))), 1,3,5 -tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione(1,3,5 -tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), methyl 3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate (methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 2,2'-oxamidobis (ethyl 3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (2,2'-oxamidobis(ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), etc. phenolicization of The compound, as an optical brightener, 0.02 to 0.035 parts by weight of 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole) (2,5-thiophenediylbis (5-tert-butyl-1,3 -benzoxazole)), 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene), 1,2-bis (5-methyl-2-benzoxazole) ethylene (1,2-bis (5-methy-2-benzoxazole) ethylene), 1,4-bis (benzoxazolyl-2-yl) naphthalene (1,4-bis (benzoxazolyl-2-yl)naphthalene), 1,4-bis (2-cyanostyryl) benzene (1,4-bis (2-cyanostyryl) benzene), 2,5-bis- (benzoxazo-2- yl) thiophene (2,5-bis- (benzoxazo-2-yl) thiophene), 5-methyl-2,2'- (vinylenedi-para-phenylene) bis-benzoxazole (5-methyl-2, 2'-(vinylenedi-para-phenylene)bisbenzoxazole) and the like, but is not limited thereto. The content of the additive is indicated based on 100 parts by weight of the ethylene copolymer.

A third aspect of the present invention is a cross-linking flame retardant thermoplastic elastomer composition of the second aspect; and a silane crosslinking masterbatch prepared by reacting vinyl-based silane with an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60 mol% by weight.

For example, the insulation coating composition may include the crosslinked flame retardant thermoplastic elastomer composition and the crosslinked masterbatch in a mass ratio of (200,000 to 350,000):(1 to 12,000), but is not limited thereto.

A fourth aspect of the present invention is a conductor sequentially from the center; an insulator layer made of the insulation coating composition of the third aspect; shielding layer; and a coating layer made of the same insulation coating composition as the insulator layer.

Hydrogen fuel-based transportation means to which the cable of the present invention can be applied include, without limitation, large-scale transportation means such as commercial vehicles, trains, or ships because long-distance driving is possible with a single charge as well as passenger cars.

A fifth aspect of the present invention supplies a polymerization solvent, ethene, alkene monomer, and diene monomer while supplying and discharging an inert gas to a continuous reactor, and injects a polymerization catalyst and an auxiliary catalyst at 1.5 to 2 atm and 80 to 110 ° C. It provides a method for producing a thermoplastic elastomer composition comprising the step of polymerizing for 4 to 20 hours under conditions.

The types of alkene monomers and diene monomers usable in the method for preparing the thermoplastic elastomer composition of the present invention are as exemplified above.

At this time, it can be carried out while supplying the polymerization solvent, ethene, alkene monomer and diene monomer in a mass ratio of (200 to 250): (28 to 36): (100 to 140): (3 to 17).

For example, the inert gas may be nitrogen, argon or hydrogen. The inert gas may be injected at a rate of 1 to 10 L/hour based on a reactor having a capacity of 350 L, but is not limited thereto, and may be appropriately changed in consideration of the capacity of the reactor to be used.

For example, the polymerization solvent may use pentane, hexane, heptane, octane, nonane, decane, etc. as a reaction medium, Not limited to this. The supply amount thereof may be selected in consideration of reactivity and/or economy. For example, it may be supplied at a rate of 20,000 to 25,000 g / hour based on a 350 L reactor, but is not limited thereto.

For example, as the polymerization catalyst, bis (indenyl) zirconium dichloride (bis (indenyl) zirconium dichloride), dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (dimethylsilylene bis (4 ,5,6,7- tetrahydroindenyl)zirconium dichloride), bis(1-methyl,3-n-butylcyclpentadienyl)zirconium dichloride (bis(1-methyl,3-n-butylcyclpentadienyl)zirconium dichloride), dimethyl Silylene bis(indenyl)zirconium dichloride, dimethylsilylene bis(2-methyl indenyl)zirconium dichloride, ethylene bisphosphorus Zirconium compounds such as ethylenebisindenylzirconium dichloride and bis(2-propylindenyl)zirconium dichloride may be used. For example, the polymerization catalyst may contain 0.01 to 0.05 mmol/ It can be injected at the speed of time, but the type and speed of the usable polymerization catalyst are not limited thereto. When the injection rate of the polymerization catalyst is lower than the above range, the yield may be low, and when it exceeds the above range, the economic efficiency of the process may decrease and the amount of catalyst residue may increase.

For example, organoaluminoxanes such as methylaluminoxane and methylisobutylaluminoxane may be used as the cocatalyst, and the cocatalyst may be injected at a rate of 0.10 to 0.30 mmol/hour. However, the type and speed of the auxiliary catalyst that can be used are not limited thereto. When the injection rate of the auxiliary catalyst is lower than the above range, the yield may be low, and when it exceeds the above range, the economic efficiency of the process may decrease and the amount of catalyst residue may increase.

After completion of the reaction, a step of recovering, separating and/or purifying the product may be further included. For example, a lower alcohol such as methanol or ethanol is added to the polymerization reaction solution recovered from the lower part of the continuous reactor to terminate the reaction, and the copolymer synthesized by steam stripping is separated from the solvent and then heated. A process of drying under reduced pressure may be additionally performed, but is not limited thereto.

A sixth aspect of the present invention is an ethylene copolymer, 18 to 24 parts by weight of the thermoplastic elastomer of claim 1 and 100 to 200 parts by weight of a flame retardant surface-treated with vinylsilane based on 100 parts by weight of the ethylene copolymer are added to a mixing mixer, and 140 to 200 parts by weight are added. A first step of producing flame-retardant thermoplastic elastomer composition pellets by extruding the melt-mixed dough at 180 ° C; And a second step of soaking the flame retardant thermoplastic elastomer composition pellets and the crosslinking agent prepared in the first step in a separate mixing mixer at a weight ratio of (14,000 to 16,500): (80 to 900) at 60 to 100 ° C.; Including, it provides a method for producing a cross-linked flame retardant thermoplastic elastomer composition.

Types of the ethylene copolymer and the crosslinking agent that can be used in the preparation method of the crosslinking type flame retardant thermoplastic elastomer composition of the present invention are as exemplified above.

Pellets produced from the first step may be produced in a size of 2 to 5 mm, but are not limited thereto. Drying and/or particle size screening of the pellets obtained after the first step may be further performed, but is not limited thereto.

The silane-treated flame retardant is prepared by adding alcohol and distilled water in a mass ratio of 90:10 to 95:3 to a reactor equipped with an agitator, and thus 10 to 50% by weight of vinyl-based silane based on the total weight of the solvent. After adding, 1000 to 2000% by weight of a flame retardant was added to a solution stirred at a speed of 50 to 300 RPM for 20 to 60 minutes while maintaining the pH of the reaction solution at 3 to 5 by adding 5 to 20% by weight of an acid catalyst. After addition, it was prepared by further stirring at a speed of 50 to 300 RPM for 20 to 120 minutes. The flame retardant is a metal hydrate-based flame retardant such as magnesium hydroxide phosphate, calcium hydroxide, aluminum hydroxide or magnesium hydroxide alone or in combination. It may be used by mixing more than one, but is not limited thereto. In addition, the metal hydrate-based flame retardant may be in the form of particles having an average particle diameter of 0.01 to 20 μm, but is not limited thereto. At this time, if the amount of vinyl-based silane is less than the above-mentioned range, the interfacial adhesion between the polymer resin and the flame retardant may deteriorate, and it is not economical to use an excessive amount. On the other hand, if the amount of the flame retardant is less than the above range, economic feasibility may be reduced, and when used in excess of the range, melt kneading properties may be deteriorated.

Furthermore, in the preparation method of the cross-linked flame-retardant thermoplastic elastomer composition of the present invention, the first step is a mercapto-type heat/oxygen antioxidant, heat-resistant antioxidant, discoloration-preventing antioxidant, and fluorescence added after the flame retardant is added. It may be performed by including one or more additives selected from the group consisting of a fluorescent whitening agent, but is not limited thereto. At this time, the type and / or content of each of the additives that can be used is as exemplified above.

A seventh aspect of the present invention is a silane crosslinking masterbatch prepared by reacting the crosslinkable flame retardant thermoplastic elastomer composition of the second aspect and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60 mol% by weight and a vinyl silane ( 220,000 to 350,000); (1 to 11,000) a first step of introducing the mixed insulation coating composition into a hopper; A second step of extruding while passing a conductor through an extruder head to which an extrusion die is attached; and a third step of crosslinking the extruded coated wire.

At this time, the second step is an extruder adjusted to 100 to 120 ° C for cylinder 1, 100 to 120 ° C for cylinder 2, 105 to 130 ° C for cylinder 3, 110 to 130 ° C for the extrusion head, and 110 to 130 ° C for the extrusion die. It can be achieved by extruding at a rate of 20 to 40 kg / hour.

For example, the silane crosslinking masterbatch is an ethylene-vinyl acetate copolymer, such as a vinyl acetate content in pellet form, in a mixing mixer such as a kneader, a Henschel mixer, or a banbury. The ethylene-vinyl acetate copolymer having a molar mass of 40 to 60% and 5 to 10 parts by weight of vinyl silane based on 100 parts by weight of the ethylene-vinyl acetate copolymer were sequentially added to produce a 10 to 10 to 10 to 10 parts by weight vinyl silane at 60 to 100 ° C. It can be prepared by soaking for 60 minutes. At this time, as the vinyl-based silane, 1,2-ethanediylbis (dimethyl (vinyl) silane) or triacetoxy (vinyl) silane [triacetoxy (vinyl) silane ], tris(methoxyethoxy)vinyl silane, dimethyl(divinyl)silane, triisopropoxy-vinylsilane, dichloromethyl vinyl silane (dichloromethyl vinyl silane), trimethoxy (vinyl) silane, and the like may be used, but are not limited thereto.

The third step is to irradiate electron beams at 1 to 2.5 MeV at 1 to 20 Mrad, use a continuous vulcanization pipe maintained at 80 to 120 ° C and 10 to 20 atm, or 60 to 100 ° C It can be performed by passing through a heating water bath of, but is not limited thereto.

An eighth aspect of the present invention includes the first step of forming a shielding layer on the outer periphery of the insulated cable of the seventh aspect; In an extruder to which a molding die is attached to the outer periphery of the insulated cable on which the shielding layer is formed, the crosslinkable flame retardant thermoplastic elastomer composition of the second aspect, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60% by mol% and vinyl (220,000 to 350,000); (1 to 11,000) Insulation coating composition mixed with a silane crosslinking masterbatch prepared by reacting silane in a hopper and extruding at a rate of 5 to 50 kg / hour A second step; And a third step of cross-linking the extruded coated wire; it provides a method for manufacturing a vehicle cable having a hydrogen fuel cell as a power source.

At this time, in the second step, cylinder 1 can be adjusted to 100 to 120 ° C, cylinder 2 to 100 to 120 ° C, cylinder 3 to 105 to 125 ° C, extrusion head to 110 to 130 ° C, and extrusion die to 110 to 130 ° C. have.

Crosslinking in the third step may be performed by the method exemplified above, but is not limited thereto.

For example, the shielding layer may be formed by taping with a metal tape or a metal coating film, or by braiding with a metal wire such as a metal wire, a metal plating wire, or an alloy wire, but is not limited thereto.

The present invention can provide an insulation coating composition with improved flexibility, flame retardancy, heat resistance, and light weight that can be replaced with conventional fuel cell vehicle insulation coating compositions and a high-voltage insulation cable manufactured therefrom, so it can be applied to high-capacity hydrogen commercial vehicles, etc. In addition to possible electrical and mechanical properties, it is possible to provide an extra-high voltage cable that combines stability, harnessability and productivity.

1 is a flowchart illustrating a method of manufacturing a cable for a hydrogen commercial vehicle according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are intended to illustrate the present invention by way of example, and the scope of the present invention is not limited to these examples.

Example 1: Preparation of cross-linked high heat resistance flame retardant thermoplastic elastomer composition 1

Step 1-1: Preparation of thermoplastic elastomer 1

Heptane 22,000 g/hour, ethene 3,000 g/hour, 1-butene 11,000 g/hour, 5-ethylidene-2-norbornene 550 While supplying at a rate of g / hour, 0.03 mmol / hour of dimethylsilylene bis (indenyl) zirconium dichloride and 0.15 mmol / hour of methylaluminoxane were introduced, and the pressure of the reactor was maintained at 1.7 atm and the temperature was 90 ° C. The polymerization reaction proceeded for 20 hours. After the reaction was completed, methanol was added to the polymerization reaction solution extracted from the bottom of the continuous reactor to terminate the reaction, and then the resulting copolymer was separated from the solvent by steam stripping and then dried at 80 ° C. for 24 hours under reduced pressure. A thermoplastic elastomer was obtained.

Step 1-2: Preparation of flame retardant surface treated with silane 1

In a reactor equipped with an agitator, 9,500 g of ethanol, 500 g of distilled water, and 1,000 g of 1,2-ethanediylbis(dimethyl(vinyl)silane) were added, and 800 g of acetic acid was added to maintain a pH of 3 to 5 while maintaining the pH at 30 RPM. 150,000 g of magnesium hydroxide having a size of 10 μm was added thereto, stirred at 100 RPM for 60 minutes, filtered, and dried at 80° C. for 24 hours to prepare a flame retardant surface-treated with silane.

Step 1-3: Preparation of silane crosslinking masterbatch 1

10,000 g of ethylene-vinyl acetate copolymer pellets having a vinyl acetate content of 40 mol% by weight and 800 g of trimethoxy (vinyl) silane were added to a Henschel mixer and soaked at 60 ° C. for 30 minutes to obtain a silane crosslinking masterbatch prepared.

Step 1-4: Preparation of flame retardant thermoplastic elastomer composition pellets 1

In a 100 L kneader mixer, 100,000 g of ethylene-vinyl acetate copolymer, 22,000 g of the thermoplastic elastomer prepared according to step 1-1, 150,000 g of flame retardant surface-treated with silane prepared according to step 1-2, zinc 2-mercaptotol Ruimidazole 3,500 g, tris(2,4-di-tert-butylphenyl)phosphite 830 g, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro cionate) 830 g and 28 g of 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) were sequentially added and melt-mixed at 150°C for 20 minutes. After being transferred to form pellets having a size of 2 to 5 mm through extrusion molding, the pellets were dried in an oven at 80° C. and selected according to particle size to prepare flame retardant thermoplastic elastomer composition pellets.

Step 1-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 1

277,188 g of the flame retardant thermoplastic elastomer composition pellets and 120 g of triallyl isocyanurate prepared in steps 1-4 were added to a Henschel mixer, and then soaked at 80 ° C. for 30 minutes to prepare crosslinked flame retardant thermoplastic elastomer composition pellets.

Step 1-6: Manufacturing of cross-linked insulated cable 1

250,000 g of the crosslinked flame retardant thermoplastic elastomer composition pellets prepared in Steps 1-5 and 1 g of the crosslinked silane masterbatch prepared in Steps 1-3 were mixed, introduced into a hopper, and placed in the head of an extruder equipped with a 5 φmm extrusion die. Cylinder 1 is 110℃, cylinder 2 is 110℃, cylinder 3 is 115℃, the extrusion head is 120℃, and the extrusion die is 120℃ After extrusion at a rate of 20 kg/hour under temperature conditions, a cross-linked insulation cable was formed by irradiating an electron beam of 10 Mrad while supplying it to a 2.5 MeV electron beam accelerator at a rate of 30 m/min.

Step 1-7: Formation of Shielding Layer 1

While passing the cross-linked insulation cable prepared in steps 1-6 through the braiding part of a conventional 32-weight braiding machine, 0.1 mm diameter tin-plated copper wire is continuously supplied to the outer periphery of the cross-linked insulation cable with a shielding rate of 80%. was formed.

Steps 1-8: Formation of Crosslinked Coating Layer 1

In a separate extruder, 250,000 g of the cross-linked flame retardant thermoplastic elastomer composition pellets prepared in accordance with steps 1-5 were put into a hopper, and the shielding layer prepared in steps 1-7 was formed on the head of the extruder to which the 8 Φ mm extrusion die was attached. While passing the insulation cable, extrude at a rate of 20 kg/hour under the temperature conditions of cylinder 1 at 110°C, cylinder 2 at 110°C, cylinder 3 at 115°C, extrusion head at 120°C, and extrusion die at 120°C. An electron beam of 10 Mrad was irradiated while being supplied to a MeV class electron beam accelerator at a rate of 30 m/min to form a crosslinked coating layer.

Example 2: Preparation of crosslinked high heat resistance flame retardant thermoplastic elastomer composition 2

Step 2-1: Production of thermoplastic elastomer 2

A thermoplastic elastomer was obtained in the same manner as in step 1-1 of Example 1.

Step 2-2: Preparation of flame retardant surface treated with silane 2

A flame retardant surface-treated with silane was prepared in the same manner as in Steps 1-2 of Example 1.

Step 2-3: Preparation of silane crosslinking masterbatch 2

A silane crosslinking masterbatch was prepared in the same manner as in Steps 1-3 of Example 1.

Step 2-4: Preparation of flame retardant thermoplastic elastomer composition pellets 2

Flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 1-4 of Example 1.

Step 2-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 2

Cross-linked flame retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 1-5 of Example 1, except that dicumyl peroxide was used instead of triallyl isocyanurate.

Step 2-6: Manufacturing of cross-linked insulated cable 2

250,000 g of the crosslinked flame retardant thermoplastic elastomer composition pellets prepared in Steps 2-5 and 1 g of the crosslinked silane masterbatch prepared in Steps 2-3 were mixed, introduced into a hopper, and placed in the head of an extruder equipped with a 5 φmm extrusion die. Cylinder 1 is 110℃, cylinder 2 is 110℃, cylinder 3 is 115℃, the extrusion head is 120℃, and the extrusion die is 120℃ While extruding at a rate of 20 kg/hour under temperature conditions, a crosslinked insulation cable was formed by passing through a curing tube maintained at 110° C. and 15 atm at a rate of 30 m/min.

Step 2-7: Formation of shielding layer 2

A shielding layer was formed in the same manner as in Steps 1-7 of Example 1, except that the cross-linked insulation cable prepared in Steps 2-6 was used.

Step 2-8: Formation of Crosslinked Coating Layer 2

In a separate extruder, 250,000 g of the cross-linked flame retardant thermoplastic elastomer composition pellets prepared according to steps 2-5 were introduced into a hopper, and the shielding layer prepared according to steps 2-7 was formed on the head of the extruder to which the 8 Φ mm extrusion die was attached. Cylinder 1 is 110℃, cylinder 2 is 110℃, cylinder 3 is 115℃, the extrusion head is 120℃, and the extrusion die is 120℃ while extruding at a rate of 20 kg/hour while passing the insulation cable at 110℃. and a vulcanization tube maintained at 15 atm at a speed of 30 m/min to form a crosslinked coating layer.

Example 3: Preparation of crosslinked high heat resistance flame retardant thermoplastic elastomer composition 3

Step 3-1: Production of thermoplastic elastomer 3

A thermoplastic elastomer was obtained in the same manner as in step 1-1 of Example 1.

Step 3-2: Preparation of flame retardant surface treated with silane 3

A flame retardant surface-treated with silane was prepared in the same manner as in Steps 1-2 of Example 1.

Step 3-3: Preparation of silane crosslinking masterbatch 3

A silane crosslinking masterbatch was prepared in the same manner as in Steps 1-3 of Example 1.

Step 3-4: Preparation of flame retardant thermoplastic elastomer composition pellets 3

Flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 1-4 of Example 1.

Step 3-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 3

Cross-linked flame retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 1-5 of Example 1, except that 830 g of dibutyltin dilaurate was used instead of triallyl isocyanurate.

Step 3-6: Production of cross-linked insulated cable 3

250,000 g of the cross-linked flame retardant thermoplastic elastomer composition pellets prepared in step 3-5 and 10,000 g of the cross-linked silane masterbatch prepared in step 3-3 were mixed, introduced into a hopper, and placed in the head of an extruder equipped with a 5 φmm extrusion die. Cylinder 1 is 110℃, cylinder 2 is 110℃, cylinder 3 is 115℃, the extrusion head is 120℃, and the extrusion die is 120℃ After extruding at a rate of 20 kg/hour under temperature conditions, a crosslinked insulated cable was formed by passing through a heating bath maintained at 95°C.

Step 3-7: Formation of Shielding Layer 3

A shielding layer was formed in the same manner as in Steps 1-7 of Example 1, except that the cross-linked insulation cable prepared in Steps 3-6 was used.

Step 3-8: Formation of Crosslinked Coating Layer 3

In a separate extruder, 250,000 g of the cross-linked flame retardant thermoplastic elastomer composition pellets prepared in steps 3-5 were put into a hopper, and the shielding layer prepared in steps 3-7 was formed on the head of the extruder to which the 8 Φ mm extrusion die was attached. While passing the insulation cable, cylinder 1 is extruded at 110°C, cylinder 2 is 110°C, cylinder 3 is 115°C, the extrusion head is 120°C, and the extrusion die is extruded at a rate of 20 kg/hour at 120°C. A crosslinked coating layer was formed by passing through a heating water bath maintained at °C.

Example 4: Preparation of crosslinked high heat resistance flame retardant thermoplastic elastomer composition 4

Step 4-1: Production of thermoplastic elastomer 4

Propene instead of 1-butene, 5-isopropylidene-2-norbordene instead of 5-ethylidene-2-norbornene, bis(1) instead of dimethylsilylene bis(indenyl)zirconium dichloride A thermoplastic elastomer was obtained in the same manner as in Step 1-1 of Example 1 except for using -methyl-3-n-butylcyclopentadienyl)zirconium dichloride.

Step 4-2: Preparation of flame retardant surface treated with silane 4

Steps 1-2 of Example 1 above, except that triacetoxy(vinyl)silane was used instead of 1,2-ethanediylbis(dimethyl(vinyl)silane) and aluminum hydroxide was used instead of magnesium hydroxide. A flame retardant surface-treated with silane was prepared in the same manner as described above.

Step 4-3: Preparation of silane crosslinking masterbatch 4

A silane crosslinking masterbatch was prepared in the same manner as in Steps 1-3 of Example 1, except that tris(methoxyethoxy)vinyl silane was used instead of trimethoxy(vinyl)silane.

Step 4-4: Preparation of flame retardant thermoplastic elastomer composition pellets 4

100,000 g of ethylene-ethyl acrylate copolymer, 22,000 g of thermoplastic elastomer prepared in step 4-1, 150,000 g of flame retardant surface-treated with silane prepared in step 4-2, 3,500 zinc 2-mercaptotoluimidazole g, tris(2,4-di-tert-butylphenyl)phosphite 830 g, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) 830 g, using 28 g of 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), preparing flame-retardant thermoplastic elastomer composition pellets in the same manner as in Steps 1-4 of Example 1 above. did

Step 4-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 4

Cross-linked flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 2-5 of Example 2, except that the flame-retardant thermoplastic elastomer composition pellets prepared in Steps 4-4 were used.

Step 4-6: Production of cross-linked insulated cable 4

Insulation crosslinked in the same manner as in Steps 2-6 of Example 2, except for using the crosslinked flame retardant thermoplastic elastomer composition pellets prepared in Steps 4-5 and the crosslinked silane masterbatch prepared in Steps 4-3. cable was formed.

Step 4-7: Formation of Shielding Layer 4

A shielding layer was formed in the same manner as in Steps 1-7 of Example 1, except for using the cross-linked insulation cable and nickel-plated copper wire prepared in Steps 4-6.

Step 4-8: Formation of Crosslinked Coating Layer 4

Steps 2-8 of Example 2 except for using the cross-linked flame-retardant thermoplastic elastomer composition pellets prepared in Steps 4-5 and the insulation cable having a shielding layer prepared in Steps 4-7 in a separate extruder. A crosslinked coating layer was formed in the same manner as above.

Example 5: Preparation of crosslinked high heat resistance flame retardant thermoplastic elastomer composition 5

Step 5-1: Production of thermoplastic elastomer 5

A thermoplastic elastomer was obtained in the same manner as in step 4-1 of Example 4.

Step 5-2: Preparation of flame retardant surface treated with silane 5

A flame retardant surface-treated with silane was prepared in the same manner as in Step 4-2 of Example 4.

Step 5-3: Preparation of silane crosslinking masterbatch 5

A silane crosslinking masterbatch was prepared in the same manner as in Steps 4-3 of Example 4.

Step 5-4: Preparation of flame retardant thermoplastic elastomer composition pellets 5

Flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 4-4 of Example 4.

Step 5-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 5

Cross-linked flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 1-5 of Example 1, except for using the flame-retardant thermoplastic elastomer composition pellets prepared in Steps 5-4.

Step 5-6: Production of cross-linked insulated cable 5

A cross-linked insulation cable was formed in the same manner as in Steps 1-6 of Example 1, except for using the composition prepared in Steps 5-5 of Example 5.

Step 5-7: Formation of Shielding Layer 5

A shielding layer was formed in the same manner as in Steps 4-7 of Example 4.

Step 5-8: Formation of Crosslinked Coating Layer 5

As in the above step 5-6, using the cross-linked flame retardant thermoplastic elastomer composition pellet prepared in step 5-5 and the insulation cable having a shielding layer prepared in step 5-7, but extruded instead of passing through the vulcanization pipe Afterwards, an electron beam of 10 Mrad was irradiated while being supplied to a 2.5 MeV electron beam accelerator at a rate of 30 m/min to form a cross-linked insulated cable.

Example 6: Preparation of cross-linked high heat resistance flame retardant thermoplastic elastomer composition 6

Step 6-1: Production of thermoplastic elastomer 6

A thermoplastic elastomer was obtained in the same manner as in step 4-1 of Example 4.

Step 6-2: Preparation of flame retardant surface treated with silane 6

A flame retardant surface-treated with silane was prepared in the same manner as in Step 4-2 of Example 4.

Step 6-3: Preparation of silane crosslinking masterbatch 6

A silane crosslinking masterbatch was prepared in the same manner as in Steps 4-3 of Example 4.

Step 6-4: Preparation of flame retardant thermoplastic elastomer composition pellets 6

Flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 4-4 of Example 4.

Step 6-5: Preparation of cross-linked flame retardant thermoplastic elastomer composition pellets 6

Cross-linked flame-retardant thermoplastic elastomer composition pellets were prepared in the same manner as in Steps 3-5 of Example 3, except for using the flame-retardant thermoplastic elastomer composition pellets prepared in Steps 6-4.

Step 6-6: Preparation of cross-linked insulated cable 6

A cross-linked insulation cable was formed in a similar manner to 3-6 of Example 3, except that the cross-linked flame retardant thermoplastic elastomer composition pellets prepared in step 6-5 were used.

Step 6-7: Formation of shielding layer 6

A shielding layer was formed in the same manner as in Steps 4-7 of Example 4.

Step 6-8: Formation of Crosslinked Coating Layer 6

As in the above step 6-6, using the cross-linked flame retardant thermoplastic elastomer composition pellet prepared in step 6-5 and the insulation cable having a shielding layer prepared in step 6-7, but extruded instead of passing through the vulcanization pipe After that, a cross-linked insulation cable was formed by passing through a heating water bath maintained at 95°C.

Comparative Example 1

In a 100 L kneader mixer, 100,000 g of ethylene-vinyl acetate copolymer, 22,000 g of low-density polyethylene, 150,000 g of magnesium hydroxide, 3,500 g of zinc 2-mercaptotoluimidazole, tris (2,4-di-tert-butylphenyl) 830 g of phosphite, 830 g of pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), and 120 g of isocyanurate were sequentially added and heated at 150 ° C. The lump dough melt-mixed for 20 minutes was transferred to a twin-screw extruder, extruded to form composition pellets having a size of 2 to 5 mm, dried in an oven at 80 ° C., and selected according to particle size to prepare composition pellets.

A crosslinked insulation cable was prepared in the same manner as in Steps 1-6 to 1-8 in Example 1, except for using 250,000 g of the prepared composition pellets, and a shielding layer was formed on the outer periphery of the crosslinked insulation cable. After that, a cross-linked coating layer was formed.

Comparative Example 2

Composition pellets were prepared in the same manner as in Comparative Example 1.

A crosslinked insulation cable was prepared in the same manner as in Steps 1-6 to 1-8 in Example 1, except for using 250,000 g of the prepared composition pellets, and a shielding layer was formed on the outer periphery of the crosslinked insulation cable. After that, a cross-linked coating layer was formed.

Experimental Example 1: Physical Property Test of Insulation Coating Composition

The insulation coating composition pellets prepared through a series of steps according to the above examples were manufactured into sheets having a thickness of 0.5 mm at a temperature of 160° C. using a hot-press. Tensile strength was measured at a speed of 100 mm/min using a universal testing machine made of dumb-bell specimens of the IEC 60811-1-1 standard. The physical properties measured for the insulation coating composition prepared as described above are shown in Table 1 below.

division Example
One Example
2 Example
3 Example
4 Example
5 Example
6 comparative example
One comparative example
2 Oxygen index (%) 34 34 35 35 34 36 28 29 The tensile strength (%) 14.8 13.2 13.9 14.0 13.2 14.5 13.0 12.8 Elongation (%) 280 272 265 275 273 288 242 230 heat resistance
(150℃×7 days) Tensile residual rate (%) 85 86 83 84 86 82 72 70 Kidney residual rate (%) 85 84 82 83 83 85 72 70 Dielectric strength (1 kv/1 minute) pass pass pass pass pass pass pass pass flexibility Great Great Great Great Great Great bad bad Heat aging discoloration (yellowing) Great Great Great Great Great Great bad bad

As shown in Table 1, the compositions of Examples 1 to 6 had an oxygen index increased by 17 to 29%, a tensile strength increased by 1.5 to 16%, and a tensile strength increased by 9.5 to 26% compared to the compositions of Comparative Examples 1 and 2. In elongation and heat resistance, tensile residual and elongation residual were increased by 14 to 23% and 14 to 22%, respectively. Furthermore, it was confirmed that all of the compositions of the above examples not only satisfied the withstand voltage conditions applicable to hydrogen commercial vehicles, but also had excellent flexibility and excellent discoloration property in which yellowing was suppressed during heat aging.

From the above description, those skilled in the art to which the present invention pertains will be able to understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential characteristics thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not limiting. The scope of the present invention should be construed as including all changes or modifications derived from the meaning and scope of the claims to be described later and equivalent concepts rather than the detailed description above are included in the scope of the present invention.

Claims (14)

A thermoplastic elastomer composition comprising ethene, alkene monomer and diene monomer,
A thermoplastic elastomer comprising the ethene, alkene monomer and diene monomer in a mass ratio of (28 to 36): (100 to 140): (3 to 17) composition.
According to claim 1,
The diene monomer is 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclo Pentyl) -2-norbornene (5- (4-cyclopentenyl) -2-norbornene), 5-cyclohexylidene-2-norbornene (5-cyclohexylidene-2-norbornene), 5-vinyl-2- Norbornene (5-vinyl-2-norbornene), 5-ethylidene-2-norbornene (ethylene-5-ethylidene-2-norbornene), 5-vinylidene-2-norbornene (5-vinylidene- 2-norbornene), and a norbornene compound selected from the group consisting of 5-methylene-2-norbornene (5-methylene-2-norbornene), the thermoplastic elastomer composition.
thermoplastic elastomers composed of ethene, alkene monomers and diene monomers;
flame retardants surface-treated with vinylsilane;
ethylene copolymer; and
cross-linking agent;
A cross-linked flame retardant thermoplastic elastomer composition comprising a.
According to claim 3,
A cross-linked flame-retardant thermoplastic elastomer composition comprising 18 to 24 parts by weight and 100 to 200 parts by weight of a thermoplastic elastomer and a flame retardant surface-treated with vinylsilane, respectively, based on 100 parts by weight of the ethylene copolymer.
According to claim 3,
A cross-linked flame-retardant thermoplastic elastomer composition comprising a thermoplastic elastomer, a flame retardant surface-treated with vinylsilane, and 0.3 to 10% by weight of a crosslinking agent based on the total weight of the ethylene copolymer.
According to claim 3,
The ethylene copolymer is ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene -A group consisting of ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, and ethylene-butyl methacrylate copolymer Which is selected from, cross-linked flame retardant thermoplastic elastomer composition.
The cross-linking flame retardant thermoplastic elastomer composition of claim 3; and
A silane crosslinking masterbatch prepared by reacting an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60 mol% by weight with a vinyl silane;
Insulation coating composition comprising a.
According to claim 7,
An insulation coating composition comprising a crosslinked flame retardant thermoplastic elastomer composition and a crosslinked masterbatch in a mass ratio of (200,000 to 350,000): (1 to 12,000).
sequentially from the center
conductor;
An insulator layer made of the insulation coating composition of claim 7;
shielding layer; and
A coating layer made of the same insulation coating composition as the insulator layer;
A cable for vehicles having a hydrogen fuel cell as a power source comprising a.
A polymerization solvent, ethene, alkene monomer, and diene monomer are supplied while inert gas is supplied to and discharged from the continuous reactor, and a polymerization catalyst and cocatalyst are introduced, and the reaction is carried out at 1.5 to 2 atmospheric pressure and 80 to 110 ° C for 4 to 20 hours. A method for producing a thermoplastic elastomer composition comprising the step of polymerizing,
The polymerization solvent, ethene, alkene monomer and diene monomer are supplied in a mass ratio of (200 to 250): (28 to 36): (100 to 140): (3 to 17), thermoplastic elastomer Method for preparing the composition.
In a mixing mixer, 18 to 24 parts by weight of the thermoplastic elastomer of claim 1 and 100 to 200 parts by weight of a flame retardant surface-treated with vinylsilane based on 100 parts by weight of the ethylene copolymer, the ethylene copolymer, and melted and mixed at 140 to 180 ° C. A first step of extruding a flame retardant thermoplastic elastomer composition to prepare pellets; and
A second step of soaking the flame retardant thermoplastic elastomer composition pellets and the crosslinking agent prepared in the first step in a separate mixing mixer at a weight ratio of (14,000 to 16,500): (80 to 900) and soaking at 60 to 100 ° C. Comprising, a method for producing a cross-linked flame retardant thermoplastic elastomer composition.
According to claim 11,
In the first step, at least one selected from the group consisting of mercapto-type thermal/oxygen antioxidants, heat-resistant antioxidants, discoloration-preventing antioxidants, and fluorescent whitening agents added after the flame retardant is added. Method for producing a cross-linked flame retardant thermoplastic elastomer composition, which is carried out by including an additive.
A silane crosslinking masterbatch prepared by reacting the crosslinkable flame retardant thermoplastic elastomer composition of claim 3 and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60 mol% by weight and a vinyl silane (220,000 to 350,000); 11,000), a first step of introducing the mixed insulation coating composition into a hopper;
A second step of extruding while passing a conductor through an extruder head to which an extrusion die is attached; and
A method for producing a cross-linked insulated cable comprising a; third step of cross-linking the extruded coated wire,
In the second step, cylinder 1 is 100 to 120 ° C, cylinder 2 is 100 to 120 ° C, cylinder 3 is 105 to 130 ° C, the extrusion head is 110 to 130 ° C, and the extrusion die is 110 to 130 ° C. To extrusion at a rate of 40 kg / hour, manufacturing method.
A first step of forming a shielding layer on the outer periphery of the insulated cable of claim 13;
The cross-linking flame-retardant thermoplastic elastomer composition of claim 3, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40 to 60% by mole and a vinyl-based extruder to which a molding die is attached to the outer periphery of the insulation cable on which the shielding layer is formed (220,000 to 350,000); (1 to 11,000) of the silane crosslinking masterbatch prepared by reacting the silane; (220,000 to 350,000); (1 to 11,000) put the insulation coating composition into a hopper and extrude at a speed of 5 to 50 kg / hour A second step; and
A method for manufacturing a vehicle cable having a hydrogen fuel cell as a power source, including a third step of crosslinking the extruded coated wire,
In the second step, cylinder 1 is 100 to 120 ° C, cylinder 2 is 100 to 120 ° C, cylinder 3 is 105 to 125 ° C, the extrusion head is 110 to 130 ° C, and the extrusion die is 110 to 130 ° C. manufacturing method.

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